US8704031B2 - Adsorptive process for separation of C8 aromatic hydrocarbons - Google Patents

Adsorptive process for separation of C8 aromatic hydrocarbons Download PDF

Info

Publication number
US8704031B2
US8704031B2 US12/827,560 US82756010A US8704031B2 US 8704031 B2 US8704031 B2 US 8704031B2 US 82756010 A US82756010 A US 82756010A US 8704031 B2 US8704031 B2 US 8704031B2
Authority
US
United States
Prior art keywords
xylene
adsorbent
para
desorbent
aromatic hydrocarbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/827,560
Other languages
English (en)
Other versions
US20120004491A1 (en
Inventor
Santi Kulprathipanja
Richard R. Willis
Annabelle Benin
John J. Low
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Assigned to UOP, LLC reassignment UOP, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LOW, JOHN J., BENIN, ANNABELLE, KULPRATHIPANJA, SANTI, WILLIS, RICHARD R.
Priority to US12/827,560 priority Critical patent/US8704031B2/en
Priority to CN201180029166.0A priority patent/CN102958878B/zh
Priority to PCT/US2011/042077 priority patent/WO2012012125A2/en
Priority to RU2012148725/05A priority patent/RU2521386C1/ru
Priority to EP11810094.0A priority patent/EP2588433A4/en
Priority to JP2013518545A priority patent/JP5592008B2/ja
Publication of US20120004491A1 publication Critical patent/US20120004491A1/en
Publication of US8704031B2 publication Critical patent/US8704031B2/en
Application granted granted Critical
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers

Definitions

  • the invention relates generally to a method for adsorptive separation of C 8 aromatic hydrocarbons. More particularly, the invention relates to a method for adsorptive separation of one compound from a mixture of C 8 aromatic hydrocarbons.
  • Simulated moving bed technology is used commercially in a number of large scale petrochemical separations.
  • the general technique employed in the performance of a simulated moving bed adsorptive separation is well described in the open literature. For instance, a general description directed to the recovery of para-xylene was presented at page 70 of the September 1970 edition of Chemical Engineering Progress (Vol. 66, No 9).
  • a generalized description of the process with an emphasis on mathematical modeling was given at the International Conference on “Fundamentals of Adsorption”, Schloss Elmau, Upper Bavaria, Germany on May 6-11, 1983, by D. B. Broughton and S. A. Gembicki. Numerous other available references describe many of the mechanical parts of a simulated moving bed system, including rotary valves for distributing various liquid flows, the internals of the adsorbent chambers, and control systems.
  • the moving bed simulation may be simply described as dividing a bed into a series of fixed beds and moving the points of introducing and withdrawing fluid streams past the series of fixed beds instead of moving the beds past the introduction and withdrawal points of the fluid streams.
  • the bed in simulated moving bed technology typically is a catalyst (for a catalyzed reaction) or an adsorbent. To carry out this simulation, it is necessary to direct a feed stream to a series of beds in sequence.
  • the number of beds often is between 12 and 24, but can be fewer or greater. These beds may be considered to be portions of a single large bed whose movement is simulated.
  • a rotary valve accomplishes the simultaneous interconnection of two separate groups of conduits through which the fluids are directed to portions of the bed.
  • a multiport rotary valve is used in simulated moving bed technology to redirect flow conduits.
  • Polyester fabrics and articles in wide use today are produced from a polymer of ethylene glycol and terephthalic acid.
  • Terephthalic acid is produced by the oxidation of para-xylene.
  • para-xylene is an important raw material in the polyester and chemical industries.
  • ortho-xylene is an important raw material in the production of phthalic anhydride, which often is used as a plasticizer in the plastics industry, and particularly in flexible polyvinyl chloride material.
  • Para-xylene can be recovered from C 8 aromatic hydrocarbons derived from various sources of aromatic hydrocarbons, such as catalytic reforming, in a number of separation processes. Liquid/liquid extraction, fractional distillation, crystallization, and adsorptive separation have been used to recover para-xylene from C 8 aromatic hydrocarbons. Other xylenes can be similarly separated from a mixture of C 8 aromatic hydrocarbons. However, para-xylene now almost exclusively is separated from C 8 aromatic hydrocarbons using simulated moving bed technology.
  • zeolites are used as adsorbent in separations of C 8 aromatic hydrocarbons.
  • U.S. Pat. No. 3,686,342 describes separation of para-xylene from a mixture of xylenes using a zeolitic adsorbent and with para-diethylbenzene as the desorbent. This is a good representation of a commercial operation.
  • zeolites often require specific operating conditions, such as hydration level, to ensure peak performance for that system. Also, improvements to selectivity of separation improved recovery of valuable product and potential improvements in downstream processing requirements.
  • aspects of this invention relate to a method for adsorptive separation of C 8 aromatic hydrocarbons. More particularly, the invention relates to a method for adsorptive separation of one compound from a mixture of C 8 aromatic hydrocarbons.
  • FIGS. 1A-1C are SEM depictions of Al-MIL-53 crystals.
  • FIGS. 2A and 2B are SEM depictions of Cr-MIL-101 crystals.
  • FIG. 3 is a photograph of Zn-MOF-5 crystals.
  • FIG. 4 is an XRD pattern of Al-MIL-53.
  • FIG. 5 is an XRD pattern of Cr-MIL-101.
  • FIG. 6 is an XRD pattern of Zn-MOF-5.
  • the invention relates to separation of C 8 aromatic hydrocarbons.
  • C 8 aromatic hydrocarbons typically means a mixture comprising para-xylene, meta-xylene, ortho-xylene, and ethylbenzene in a mutual solvent.
  • the invention relates to separation of binary or ternary mixtures as well.
  • An embodiment of the invention is directed to a method for adsorptive separation of one compound from a mixture of C 8 aromatic hydrocarbons. Another embodiment of the invention is directed to adsorptive separation of para-xylene from a mixture of C 8 aromatic hydrocarbons. Still another embodiment of the invention is directed to adsorptive separation of ortho-xylene from a mixture of C 8 aromatic hydrocarbons. In particular, embodiments of the invention are directed to a method for adsorptive separation of para-xylene or of ortho-xylene from a mixture of C 8 aromatic hydrocarbons using a metal organic framework adsorbent in a simulated moving bed process.
  • the inventors have discovered metal organic frameworks that selectively recover para-xylene and metal organic frameworks that selectively recover ortho-xylene from C 8 aromatic hydrocarbons.
  • the target compound then is desorbed from the metal organic framework and the resultant stream then further processed in accordance with known methods to recover purified target compound.
  • aspects of the invention relate to selective adsorption of C 8 aromatic hydrocarbons by metal organic frameworks
  • embodiments of the invention will be described with particularity as they relate to recovery of one xylene from C 8 aromatic hydrocarbons.
  • embodiments of the invention will be described as they relate to adsorption of para-xylene from C 8 aromatic hydrocarbons using metal organic frameworks and simulated moving bed technology.
  • Another particular embodiment of the invention relating to adsorption of ortho-xylene from C 8 aromatic hydrocarbons using metal organic frameworks and simulated moving bed technology will be described.
  • Para-xylene is separated from xylene mixtures almost exclusively using simulated moving bed (SMB) technology.
  • SMB process is a commercial adsorptive separation process using several adsorption beds and moving the inlet streams and outlet streams between the beds, where a process stream comprising para-xylene is passed through the beds.
  • the adsorption beds comprise an adsorbent for preferentially adsorbing the para-xylene and later desorbing the para-xylene using a desorbent as the process stream.
  • Ortho-xylene is similarly recovered under similar operating conditions but with different adsorptive MOF material.
  • a “feed mixture” is a mixture containing one or more extract components, herein para-xylene, and one or more raffinate components to be separated by the process.
  • feed stream indicates a stream of a feed mixture which is passed into contact with the MOF adsorbent used in the process.
  • An “extract component” is para-xylene, which is more selectively adsorbed by the adsorbent, while a “raffinate component” is a compound or type of compound that is less selectively adsorbed.
  • desorbent compound means generally a material capable of desorbing para-xylene from the adsorbent.
  • raffinate stream or “raffinate output stream” means a stream in which a raffinate component is removed from the adsorbent bed after the adsorption of para-xylene.
  • the composition of the raffinate stream can vary from essentially 100% desorbent material to essentially 100% raffinate components.
  • extract stream or “extract output stream” means a stream in which para-xylene, which has been desorbed by a desorbent material, is removed from the adsorbent bed.
  • the composition of the extract stream can vary from essentially 100 percent desorbent material to essentially 100 percent para-xylene.
  • Simulated moving bed technology uses established commercial technology wherein beds of the adsorbent are held in place in one or more typically cylindrical adsorbent chambers and the positions at which the streams involved in the process enter and leave the chambers are slowly shifted along the length of the beds.
  • An SMB process produces at least two effluent streams; an extract stream containing a compound which was selectively retained on the adsorbent and a raffinate stream containing compounds not adsorbed. Both the extract and the raffinate streams will also contain the desorbent compound(s). The concentration of the desorbent in the extract and raffinate stream will vary somewhat with time during each incremental shifting of the process bed lines due several factors.
  • the extract and raffinate streams typically are passed into extract and raffinate fractionation columns, in which the desorbent is separated from the extract and raffinate compounds. The desorbent is in this way recovered, and it is then recirculated to the adsorption zone as a process stream referred to herein as the desorbent stream.
  • a feed mixture comprising two or more C 8 aromatic hydrocarbons.
  • the feed contains para-xylene, meta-xylene, ortho-xylene, and ethylbenzene in solvent.
  • the properties and characteristics of suitable solvents are set forth below.
  • the bed is MOF adsorbent, typically Al-MIL-53 or Zn-MOF-5, which adsorbs para-xylene while permitting meta-xylene, ortho-xylene, ethylbenzene, and the solvent to essentially pass through the adsorption zone in an unchanged condition and become part of a raffinate stream.
  • the flow of the feed stream through the adsorbent bed is stopped and the adsorption zone then is flushed to remove nonadsorbed materials surrounding the adsorbent. Thereafter, the adsorbed hydrocarbon is desorbed from the adsorbent by passing a desorbent stream through the adsorbent bed, forming an extract stream.
  • the desorbent material is commonly also used to flush nonadsorbed materials from the void spaces around and within the adsorbent. Both the raffinate and extract stream contain the desorbent compound(s) and are fractionated to recover the desorbent.
  • extract product and raffinate product mean streams produced by the process containing, respectively, an extract component and a raffinate component in higher concentrations than those found in the extract stream and the raffinate stream withdrawn from adsorbent chamber.
  • the extract stream may be rich in the desired compound or may only contain an increased concentration.
  • rich is intended to indicate a concentration of the indicated compound or class of compounds greater than 50 mole percent.
  • Zone I the adsorption zone.
  • Zone II liquid which contains the undesired isomer(s), that is, with raffinate.
  • This liquid is removed from the adsorbent in Zone II, referred to as a purification zone.
  • the undesired raffinate components are flushed from the void volume of the adsorbent bed by a material which is easily separated from the desired component by fractional distillation.
  • Zone III of the adsorbent chamber(s) the para-xylene is released from the adsorbent by exposing and flushing the adsorbent with the desorbent (mobile phase). The released para-xylene and accompanying desorbent are removed from the adsorbent in the form of the extract stream.
  • Zone IV is a portion of the adsorbent located between Zones I and III which is used to segregate Zones I and III.
  • desorbent is partially removed from the adsorbent by a flowing mixture of desorbent and undesired components of the feed stream. The liquid flow through Zone IV prevents contamination of Zone III by Zone I liquid by flow cocurrent to the simulated motion of the adsorbent from Zone III toward Zone I.
  • upstream and downstream are used herein in their normal sense and are interpreted based upon the overall direction in which liquid is flowing in the adsorbent chamber. That is, if liquid is generally flowing downward through a vertical adsorbent chamber, then upstream is equivalent to an upward or higher location in the chamber.
  • F volumetric feed rate of the feed mixture
  • Embodiments of the invention typically operate at a performance index above about 90 at an A/F ratio of from about 0.5 to about 0.7.
  • Desorbent purity allows operation at an L 3 /A ratio of about 1.6 to about 2.3.
  • the A/F ratio sets an operating curve, specific to a particular L 3 rate.
  • the simulated moving bed process for embodiments of the invention is operated with an A/F ratio of about 0.5 to about 0.7.
  • a process unit designed for normally producing a high purity product e.g. 99 percent
  • Units designed to produce low purity product having about 80-85 percent purity will operate in the lower end of this range.
  • the operating conditions interact such that overall optimum performance requires balancing the effects of several conditions.
  • increasing the L 3 /A ratio increases recovery but requires more desorbent circulation. It is to be noted that it is normally preferred to minimize both L 3 and A, which leads to a need to balance initial design and operations.
  • a ratio of L 3 /A of from about 1.6 to about 2.3 is typical.
  • Volumetric ratio of desorbent to feed (D/F) typically influences overall performance. The D/F ratio often is varied, depending on feed composition, target performance levels, and desired adsorption zone operating temperature. Desorbent purity also can be considered as an operating variable.
  • adsorption and desorption steps can be performed in a single large bed of adsorbent or in several parallel beds on a swing bed basis.
  • simulated moving bed adsorptive separation provides several advantages, such as high purity and recovery. Therefore, many commercial scale petrochemical separations, especially those for the separation of xylenes and mixed normal paraffins are performed using simulated moving bed technology.
  • the previously sited references are incorporated for their teaching on the performance of this technique. Further details on equipment and techniques for using in an SMB process may be found in U.S. Pat. Nos.
  • the adsorbent chambers of the adsorption zone and other portions of the process can be operated at conventional conditions using otherwise standard equipment.
  • the desorbent is selected to suitably desorb target material from the adsorbent, and so adsorbent and desorbent are linked. The performance of the overall process is dependent on both, so desorbent must be selected carefully.
  • Desorbents are not normally fungible, or interchangeable. That is, a desorbent that functions well with one adsorbent will not necessarily give good results when used with a different adsorbent.
  • Adsorbents for this process in simulated moving bed technology are MOF's, particularly Al-MIL-53, Cr-MIL-101, particularly for para-xylene, and Zn-MOF-5 particularly for ortho-xylene.
  • Desorbent used in the subject process is often is benzene, indan, and substituted alkylbenzenes, where the alkyl moieties have between 1 and 5 carbon atoms.
  • the substituted alkylbenzenes include para-diethylbenzene, toluene, and 1,4-diisopropylbenzene.
  • the choice of an adsorbent-desorbent system is normally governed by economic factors which in turn are controlled by performance of the adsorbent-desorbent pair in terms of recovery and purity at specific conditions and for specific feed compositions. Therefore, most typical operating conditions expressed herein are determined by technology factors such as adsorbent capability and economic factors such as the desired product and its purity. These preferences will vary with the economic and business situation of specific units.
  • Operating conditions may be set by several considerations. For instance, there is often a tradeoff between higher recovery at higher temperatures and higher purity at lower temperatures.
  • Adsorption promoting conditions also include a pressure sufficient to maintain the process fluids in liquid phase; which may be from about atmospheric to 600 psig.
  • Desorption conditions generally include the same temperatures and pressure as used for adsorption conditions.
  • the practice of the subject invention requires no significant variation in operating conditions, adsorbent or desorbent composition within the adsorbent chambers. That is, the adsorbent in a chamber preferably remains at the same temperature throughout the process.
  • the A/F ratio is a separate design variable which greatly affects the performance of the process and the cost of the process unit.
  • A relates directly to the quantity of adsorbent retained in the adsorbent chambers
  • a high A/F ratio leads directly to the need for a larger unit to accommodate the adsorbent.
  • the cost of the adsorbent itself also increases. Therefore it is desired to operate at a minimum acceptable A/F ratio.
  • the ratio of L 3 /A is minimized.
  • L 3 can basically be varied only by varying the flow rate of the desorbent. Minimizing this flow reduces required fluid flows, which allows for smaller transfer lines and reduced size and operating costs for the extract and raffinate columns.
  • Performance measured by both selectivity and capacity, varies greatly between different adsorbent/desorbent systems, and is affected by feed composition and the operating conditions.
  • the adsorption zone is operated at conditions which include a temperature below about 200° C., as this provides better selectivity and capacity. Often, the temperature is maintained in the range of about 100° C. to about 190° C., and more often between about 120° C. and about 177° C.
  • An important characteristic of an adsorbent is the rate of exchange of the desorbent for para-xylene of the feed mixture materials or, in other words, the relative rate of adsorption/desorption of the para-xylene. This characteristic relates directly to the amount of desorbent material that must be employed in the process to recover the para-xylene from the adsorbent. Faster rates of exchange reduce the amount of desorbent material needed to remove the para-xylene, and, therefore, permit a reduction in the operating cost of the process. With faster rates of exchange, less desorbent material has to be pumped through the process and separated from the extract stream for reuse in the process. Exchange rates are often temperature dependent.
  • desorbent materials should have a selectivity equal to about 1 or slightly less than 1 with respect to all extract components so that all of the extract components can be desorbed as a class with reasonable flow rates of desorbent material, and so that extract components can later displace desorbent material in a subsequent adsorption step.
  • the desorbent material In adsorptive separation processes, which are generally operated continuously at substantially constant pressures and a temperature which insures liquid phase, the desorbent material must be judiciously selected to satisfy many criteria.
  • the desorbent material should displace an extract component from the adsorbent with reasonable mass flow rates without itself being so strongly adsorbed as to unduly prevent an extract component from displacing the desorbent material in a following adsorption cycle.
  • the selectivity it is preferred that the adsorbent be more selective for all of the extract components with respect to a raffinate component than it is for the desorbent material with respect to a raffinate component.
  • desorbent materials must be compatible with the particular adsorbent and the particular feed mixture.
  • desorbent materials should not chemically react with or cause a chemical reaction of either an extract component or a raffinate component. Both the extract stream and the raffinate stream are typically removed from the adsorbent void volume in admixture with desorbent material and any chemical reaction involving a desorbent material and an extract component or a raffinate component or both would complicate or prevent product recovery.
  • the desorbent should also be easily separated from the extract and raffinate components, as by fractionation.
  • desorbent materials should be readily available and reasonable in cost.
  • An embodiment of the invention is directed to separation of para-xylene from C 8 aromatic hydrocarbons by passing C 8 aromatic hydrocarbons over metal organic framework that preferentially adsorbs para-xylene from the mixture.
  • the metal organic framework is selected from the group consisting of Al-MIL-53, Zn-MOF-5, and blends thereof. Most typically, the metal organic framework is Al-MIL-53.
  • Another embodiment of the invention is directed to separation of ortho-xylene from C 8 aromatic hydrocarbons by passing C 8 aromatic hydrocarbons over metal organic framework that preferentially adsorbs ortho-xylene from the mixture.
  • the metal organic framework is Cr-MIL-101.
  • Each of the identified metal organic frameworks is synthesized in accordance with known techniques. Generally, a solution of a transition metal salt and an organic bidentate ligand is reacted, optionally in the presence of an acid catalyst, at a temperature and for a time sufficient to form crystals comprising the metal organic framework.
  • an acid catalyst optionally in the presence of an acid catalyst
  • the resultant crystals then are washed, filtered, and further processed in accordance with known methods and techniques to obtain metal organic framework crystals suitable for use in embodiments of the invention.
  • the skilled practitioner recognizes that other methods of making these metal organic framework crystals also will produce metal organic framework crystals suitable for use in embodiments of the invention. With the guidance provided herein, the skilled practitioner can make suitable metal organic framework crystals.
  • Methods for forming the crystalline powders into such agglomerates include the addition of a binder to a high purity adsorbent powder in a wet mixture.
  • the binder aids in forming or agglomerating the crystalline particles.
  • the blended binder-adsorbent mixture may be extruded into cylindrical pellets or formed into beads which are subsequently treated in order to convert the binder to a binder of considerable mechanical strength.
  • the adsorbent may also be bound into irregular shaped particles formed by spray drying or crushing of larger masses followed by size screening.
  • the adsorbent particles may thus be in the form of extrudates, tablets, spheres or granules having a desired particle range, preferably from about 16 to about 60 mesh (Standard U.S. Mesh) (1.9 mm to 250 microns).
  • Water permeable organic polymers are generally used as binders.
  • the metal organic framework crystals ordinarily will be in the form of small crystals present in the adsorbent particles in amounts ranging from about 75 wt percent to about 100 wt percent of the particle based on as-prepared composition.
  • the remainder of the adsorbent typically will be the matrix of the binder present in intimate mixture with the small particles of the adsorbent material.
  • This matrix material may be an adjunct of the manufacturing process for the MOF, for example, from the intentionally incomplete purification of the MOF during its manufacture. With the guidance provided herein, the skilled practitioner will be able to select a binder and form adsorbent particles.
  • Embodiments of the invention are directed to separation of para-xylene from C 8 aromatic hydrocarbons.
  • X A is the amount, in weight percent, of component A adsorbed
  • X B is the amount, in weight percent, of component B adsorbed
  • C A is the equilibrium concentration of component A in the external liquid phase
  • C B is the equilibrium concentration of component B in the external liquid phase, wherein these values are measured in the presence of C 8 aromatic hydrocarbons in a competitive adsorption isotherm evaluation.
  • Embodiments of the invention are directed to use of metal organic framework crystals that exhibit a selectivity thus calculated of at least about 1.1, more typically at least about 1.3, and most typically at least about 1.5, as, as adsorbent for one compound of C 8 aromatic hydrocarbons.
  • the metal organic framework crystals normally are used in the form of particulate agglomerates having higher physical strength and attrition resistance than the active components themselves.
  • the agglomerates contain the active adsorptive material dispersed in an amorphous matrix or binder, having channels and cavities therein which enable fluid to access the adsorptive material, as described above.
  • Crystals of Al-MIL-53, Cr-MIL-101, and Zn-MOF-5 were made by preparing for each a solution of a transition metal salt and H 2 BDC.
  • the transition metal salt and H 2 DBC were reacted at the temperature and for the time set forth in the following Table 2:
  • FIGS. 1A-1C Crystals of Al-MIL-53 produced in accordance with the method set forth in Table 1 above are depicted in FIGS. 1A-1C . These figures illustrate the linear lattice characteristic of Al-MIL-53. In particular, FIGS. 1B and 1C illustrate the folded linear structure expected of this product after activation.
  • FIGS. 2A and 2B Crystals of Cr-MIL-101 produced in accordance with the method set forth in Table 1 above are depicted in FIGS. 2A and 2B , which illustrate the rhombic crystalline form characteristic of Cr-MIL-101.
  • FIG. 3A Crystals of Zn-MOF-5 produced in accordance with the method set forth in Table 1 above are depicted in FIG. 3A , which illustrates the rectangular, cubic crystalline form characteristic of Zn-MOF-5.
  • the adsorbent metal organic framework crystals synthesized in Example 1 were subjected to separate liquid phase competitive adsorption isotherm evaluations.
  • a quantity of metal organic framework crystals was tumbled in a sealed vial with a quantity of feed comprising para-xylene, meta-xylene, ortho-xylene, and ethylbenzene in cyclohexane.
  • a control comprising a vial of the same quantity of feed also was prepared.
  • the vials were tumbled overnight (about 12 hours) at room temperature.
  • the quantities of adsorbent and feed, the composition of the feed, and the volume of the vial for each MOF is set forth in Table 4, as follows:
  • Cr-MIL-101 has pores 2.6 Angstroms by 13.6 Angstroms and 8.5 Angstroms with 1D channels.
  • embodiments of the invention can be directed to separation of C 8 aromatic hydrocarbons from a different solvent.
  • embodiments of the invention include separate recovery of ortho-xylene.
  • embodiments of the invention can be directed to separation of binary mixtures.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US12/827,560 2010-06-30 2010-06-30 Adsorptive process for separation of C8 aromatic hydrocarbons Expired - Fee Related US8704031B2 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US12/827,560 US8704031B2 (en) 2010-06-30 2010-06-30 Adsorptive process for separation of C8 aromatic hydrocarbons
EP11810094.0A EP2588433A4 (en) 2010-06-30 2011-06-28 ADSORPTION PROCESS FOR SEPARATING C8 AROMATIC HYDROCARBONS
PCT/US2011/042077 WO2012012125A2 (en) 2010-06-30 2011-06-28 Adsorptive process for separation of c8 aromatic hydrocarbons
RU2012148725/05A RU2521386C1 (ru) 2010-06-30 2011-06-28 Адсорбционный способ разделения c8 ароматических углеводородов
CN201180029166.0A CN102958878B (zh) 2010-06-30 2011-06-28 分离c8芳烃的吸附工艺
JP2013518545A JP5592008B2 (ja) 2010-06-30 2011-06-28 Ｃ８芳香族炭化水素の分離のための吸着プロセス

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12/827,560 US8704031B2 (en) 2010-06-30 2010-06-30 Adsorptive process for separation of C8 aromatic hydrocarbons

Publications (2)

Publication Number Publication Date
US20120004491A1 US20120004491A1 (en) 2012-01-05
US8704031B2 true US8704031B2 (en) 2014-04-22

Family

ID=45400214

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/827,560 Expired - Fee Related US8704031B2 (en) 2010-06-30 2010-06-30 Adsorptive process for separation of C8 aromatic hydrocarbons

Country Status (6)

Country Link
US (1) US8704031B2 (zh)
EP (1) EP2588433A4 (zh)
JP (1) JP5592008B2 (zh)
CN (1) CN102958878B (zh)
RU (1) RU2521386C1 (zh)
WO (1) WO2012012125A2 (zh)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017048378A1 (en) 2015-09-17 2017-03-23 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene using a metal organic framework adsorbent in a simulated moving-bed process
WO2017146914A1 (en) 2016-02-26 2017-08-31 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene
WO2017201159A1 (en) 2016-05-20 2017-11-23 Exxonmobil Chemical Patents Inc. Xylene separation process
WO2021173238A1 (en) 2020-02-27 2021-09-02 Exxonmobil Chemical Patents Inc. Xylene separation processes using a membrane separator
US20230141078A1 (en) * 2020-04-02 2023-05-11 Zhejiang University Method for separating c8 aromatic hydrocarbon isomer mixture

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201215693D0 (en) * 2012-09-03 2012-10-17 Univ Liverpool Metal-organic framework
US9302955B2 (en) 2013-09-27 2016-04-05 Uop Llc Systems and methods for separating xylene isomers using selective adsorption
US9950972B2 (en) 2013-09-27 2018-04-24 Uop Llc Apparatuses and methods for forming C8 aromatic streams with selected amounts of C9 aromatics
US9326150B2 (en) * 2013-11-05 2016-04-26 Microsoft Technology Licensing, Llc Community Wi-Fi network joined access point configuration
WO2015188199A1 (en) * 2014-06-06 2015-12-10 Northwestern University Carbohydrate-mediated purification of petrochemicals
CN107537457A (zh) * 2016-11-17 2018-01-05 天津工业大学 采用"一锅法"制备具有mtn沸石构型的新型复合材料
CN107529451A (zh) * 2016-11-17 2018-01-02 天津工业大学 采用"一锅法"制备具有一维孔道和催化活性的新型复合材料
CN107519841A (zh) * 2016-11-17 2017-12-29 天津工业大学 采用"一锅法"制备具有吸附和催化降解活性的介孔复合材料
CN107519942A (zh) * 2016-11-17 2017-12-29 天津工业大学 采用"一锅法"制备具有呼吸效应的新型复合材料
CN110961080B (zh) * 2018-09-29 2022-06-28 中国石油化工股份有限公司 一种吸附分离c8芳烃的吸附剂及其制备方法
CN110237816B (zh) * 2019-06-13 2022-06-17 江苏科技大学 一种硝酸银修饰的金属有机骨架吸附材料的制备方法及其应用
CN112110786B (zh) * 2019-06-21 2023-08-01 辽宁科技大学 分离二甲苯同分异构体混合物的制备液相色谱法
CN112110787B (zh) * 2019-06-21 2022-09-27 辽宁科技大学 分离二甲苯同分异构体混合物的模拟移动床色谱法
CN110283033B (zh) * 2019-06-28 2021-11-02 中国石油天然气集团有限公司 多区协控微循环高容量吸附结晶耦合芳烃生产方法及系统
EP4154966A4 (en) * 2021-02-03 2023-07-19 Zhejiang University MIXED XYLENE SEPARATION PROCESS

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395951B1 (en) * 2000-09-26 2002-05-28 Uop Llc Adsorptive separation product recovery by fractional distillation
US6706938B2 (en) 2000-11-16 2004-03-16 Uop Llc Adsorptive separation process for recovery of para-xylene
US20060210458A1 (en) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Liquid absorption by metal-organic frameworks
US7396973B1 (en) * 2005-02-02 2008-07-08 Winter George R Simulated moving bed adsorptive separation process for handling multiple feedstocks
US20090131643A1 (en) 2006-04-14 2009-05-21 Zheng Ni Rapid metal organic framework molecule synthesis method
WO2009077670A1 (fr) 2007-10-01 2009-06-25 Centre National De La Recherche Scientifique - Cnrs Nanoparticules hybrides organiques inorganiques a base de carboxylates de fer
WO2009077671A1 (fr) 2007-10-01 2009-06-25 Centre National De La Recherche Scientifique - Cnrs Solide hybride organique inorganique a surface modifiee
US20090263621A1 (en) 2006-12-13 2009-10-22 Korea Research Institute Of Chemical Technology Porous organic-inorganic hybrid materials and adsorbent comprising the same
WO2009130251A2 (en) 2008-04-22 2009-10-29 Faculte Polytechnique De Mons Gas adsorbent
US7638677B2 (en) 2006-09-22 2009-12-29 Uop Llc Mixed matrix adsorbent for para-xylene separation
US20100064888A1 (en) 2006-10-30 2010-03-18 Basf Se Aluminum naphthalenedicarboxylate as porous metal-organic framework material

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3686342A (en) 1970-09-18 1972-08-22 Universal Oil Prod Co Aromatic hydrocarbon separation by adsorption
ZA76937B (en) * 1975-03-27 1977-04-27 Uop Inc Aromatic hydrocarbon isomer separation process
US4283587A (en) * 1980-06-16 1981-08-11 Uop Inc. Adsorptive separation of aromatic isomers
US4376226A (en) * 1982-02-05 1983-03-08 Exxon Research & Engineering Co. Process for the separation of ortho aromatic isomers by selective adsorption
JPH08217700A (ja) * 1995-02-13 1996-08-27 Chiyoda Corp パラキシレンの分離方法
KR101591544B1 (ko) * 2008-06-26 2016-02-03 유오피 엘엘씨 Ｃ8 및 ｃ9 방향족 탄화수소의 혼합물로부터 파라-크실렌을 분리하기 위한 방법 및 장치
US7812208B2 (en) * 2008-09-22 2010-10-12 Uop Llc Binderless adsorbents with improved mass transfer properties and their use in the adsorptive separation of para-xylene

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6395951B1 (en) * 2000-09-26 2002-05-28 Uop Llc Adsorptive separation product recovery by fractional distillation
US6706938B2 (en) 2000-11-16 2004-03-16 Uop Llc Adsorptive separation process for recovery of para-xylene
US7396973B1 (en) * 2005-02-02 2008-07-08 Winter George R Simulated moving bed adsorptive separation process for handling multiple feedstocks
US20060210458A1 (en) * 2005-03-16 2006-09-21 Basf Aktiengesellschaft Liquid absorption by metal-organic frameworks
US7534303B2 (en) 2005-03-16 2009-05-19 Basf Aktiengesellschaft Liquid absorption by metal-organic frameworks
US20090131643A1 (en) 2006-04-14 2009-05-21 Zheng Ni Rapid metal organic framework molecule synthesis method
US7638677B2 (en) 2006-09-22 2009-12-29 Uop Llc Mixed matrix adsorbent for para-xylene separation
US20100064888A1 (en) 2006-10-30 2010-03-18 Basf Se Aluminum naphthalenedicarboxylate as porous metal-organic framework material
US20090263621A1 (en) 2006-12-13 2009-10-22 Korea Research Institute Of Chemical Technology Porous organic-inorganic hybrid materials and adsorbent comprising the same
WO2009077670A1 (fr) 2007-10-01 2009-06-25 Centre National De La Recherche Scientifique - Cnrs Nanoparticules hybrides organiques inorganiques a base de carboxylates de fer
WO2009077671A1 (fr) 2007-10-01 2009-06-25 Centre National De La Recherche Scientifique - Cnrs Solide hybride organique inorganique a surface modifiee
WO2009130251A2 (en) 2008-04-22 2009-10-29 Faculte Polytechnique De Mons Gas adsorbent

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Alaerts, et al., "Metal-organic frameworks as high-potential adsorbents for liquid phase separations of olefins, alkylnaphthalenes and dichlorobenzenes", Physical Chemistry Chemical Physics, vol. 11, No. 16, pp. 2903-2911, 2009.
Alaerts, et al., "Selective Adsorption and Separation of ortho-Substituted Akylaromatics with Microporous Aluminum Terephthalate MIL-53", Journal of the American Chemical Society, vol. 130, No. 43, pp. 14170-14178, 2008.
Basu, et al., "Solvent resistant nanofiltration (SRNF) membranes based on metal organic frameworks", Journal of Membrane Science, vol. 344, pp. 190-198, Nov. 2009.
Finsy et al., "Framework Breathing in the Vapour-Phase Adsorption and Separation of Xylene Isomers with the Metal-Organic Framework MIL-53", Chemistry-A European Journal, vol. 15, No. 31, pp. 7724-7731, Aug. 3, 2009.
Finsy, et al., "Separation of CO2/CH4 mixtures with the MIL-53(Al) metal-organic framework", Microporous and Mesoporous Materials, vol. 120, No. 3, pp. 221-227, Apr. 15, 2009.
Gu, "Metal-Organic Framework MIL-101 for High-Resolution Gas-Chromatographic Separation of Xylene Isomers and Ethylbenzene", Angew. Chem. Int. Ed. 2010, 49, 1477-1480.
Gu, et al., "Adsorption and Separation of Xylene Isomers and Ethylbenzene on Two Zn-Terephthalate Metal-Organic Frameworks", The Journal of Physical Chemistry, American Chemical Society, vol. 114, pp. 311-316, Dec. 14, 2009.
Moreira, "Influence of the Eluent in the MIL-53(Al) Selectivity for Xylene Isomers Separation", Ind. Eng. Chem. Res. 2011, 50, 7688-7695.
Trung, et al., "Hydorcarbon Adsorption in the Flexible Metal Organic Frameworks MIL-53(Al, Cr)", Journal of the American Chemical Society, vol. 130, No. 50, pp. 16926-16932, Dec. 17, 2008.

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017048378A1 (en) 2015-09-17 2017-03-23 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene using a metal organic framework adsorbent in a simulated moving-bed process
WO2017146914A1 (en) 2016-02-26 2017-08-31 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene
US10906851B2 (en) 2016-02-26 2021-02-02 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene
WO2017201159A1 (en) 2016-05-20 2017-11-23 Exxonmobil Chemical Patents Inc. Xylene separation process
WO2021173238A1 (en) 2020-02-27 2021-09-02 Exxonmobil Chemical Patents Inc. Xylene separation processes using a membrane separator
US11673848B2 (en) 2020-02-27 2023-06-13 Exxonmobil Chemical Patents Inc. Xylene separation processes using a membrane separator
US20230141078A1 (en) * 2020-04-02 2023-05-11 Zhejiang University Method for separating c8 aromatic hydrocarbon isomer mixture
US12077496B2 (en) * 2020-04-02 2024-09-03 Zhejiang University Method for separating C8 aromatic hydrocarbon isomer mixture

Also Published As

Publication number Publication date
RU2012148725A (ru) 2014-05-20
WO2012012125A3 (en) 2012-03-29
US20120004491A1 (en) 2012-01-05
EP2588433A4 (en) 2014-01-01
RU2521386C1 (ru) 2014-06-27
WO2012012125A2 (en) 2012-01-26
EP2588433A2 (en) 2013-05-08
CN102958878B (zh) 2014-12-31
JP2013531676A (ja) 2013-08-08
CN102958878A (zh) 2013-03-06
JP5592008B2 (ja) 2014-09-17

Similar Documents

Publication Publication Date Title
US8704031B2 (en) Adsorptive process for separation of C8 aromatic hydrocarbons
US6706938B2 (en) Adsorptive separation process for recovery of para-xylene
JP4871887B2 (ja) 擬似移動床吸着からの改良された生成物回収方法
CA1190482A (en) Process for separating normal paraffins
KR20110076867A (ko) 개선된 물질 전달 특성을 갖는 무바인더 흡착제 및 파라-크실렌의 흡착 분리에서의 이의 용도
CN111410596B (zh) 一种碳八芳烃同分异构体混合物的分离方法
EP1060776B1 (en) Use of raffinate line flush in a simulated continuous moving bed adsorptive separation process
US8609925B2 (en) Adsorbents with improved mass transfer properties and their use in the adsorptive separation of para-xylene
US7638677B2 (en) Mixed matrix adsorbent for para-xylene separation
EP0683148B1 (en) Process for the separation of ethylbenzene by adsorption on cesium exchanged zeolite X
CN114409498A (zh) 从碳八芳烃同分异构体混合物中优先吸附分离乙苯的方法
US4467126A (en) Process for the separation of di-substituted benzene
JPS6310747A (ja) トルエンジアミン異性体の分離方法
US20140179975A1 (en) Split-shell raffinate columns and methods for use in continuous adsorptive separation processes
CN110683931B (zh) 一种pvdc树脂衍生微孔碳材料在吸附分离二甲苯异构体上的应用
CN106883092B (zh) 一种吸附分离烷基芳烃异构体的方法
JP2002540178A (ja) エーテルを脱着剤として使用するパラ−キシレンの分離法
JP2023528610A (ja) 混合キシレンを分離する方法
CN108997076A (zh) 从二甲苯混合物中分离对二甲苯的方法
KR20180104570A (ko) 크실렌의 모사 이동층 분리를 위한 프로세스, 및 최적화된 작동 조건
AU3497599A (en) Use of raffinate line flush in a simulated continuous moving bed adsorptive separation process
JPH0639428B2 (ja) ２，６―ｄｅｔまたは３，５―ｄｅｔをそれ等と他のｄｅｔ異性体との混合物から回収するためのクロマトグラフ分離法

Legal Events

Date Code Title Description
AS Assignment

Owner name: UOP, LLC, ILLINOIS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KULPRATHIPANJA, SANTI;WILLIS, RICHARD R.;BENIN, ANNABELLE;AND OTHERS;SIGNING DATES FROM 20100629 TO 20100630;REEL/FRAME:024619/0223

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551)

Year of fee payment: 4

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20220422